CN104961757A - Method for preparing metal organic framework material by using fly ash - Google Patents
Method for preparing metal organic framework material by using fly ash Download PDFInfo
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- CN104961757A CN104961757A CN201510284334.0A CN201510284334A CN104961757A CN 104961757 A CN104961757 A CN 104961757A CN 201510284334 A CN201510284334 A CN 201510284334A CN 104961757 A CN104961757 A CN 104961757A
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- organic framework
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 27
- 239000010881 fly ash Substances 0.000 title claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 45
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims description 24
- 230000008025 crystallization Effects 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000010883 coal ash Substances 0.000 claims description 14
- -1 Iron protochloride tetrahydrate Chemical class 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910001447 ferric ion Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013384 organic framework Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000013122 aluminium-based metal-organic framework Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 229960002089 ferrous chloride Drugs 0.000 abstract 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000013206 MIL-53 Substances 0.000 description 2
- 239000013118 MOF-74-type framework Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a method for preparing a metal organic framework material by using fly ash, wherein the method comprises fly ash dissolving, aluminum trichloride crystal obtaining, ferrous chloride tetrahydrate obtaining and metal organic framework material obtaining. With the metal organic framework material preparation method of the present invention, the new conversion approach is provided for the resource of the fly ash, and the metal organic framework material prepared through the method has the large specific surface area.
Description
Technical field
The present invention relates to the preparation method of metal-organic framework material, be specifically related to a kind of coal ash for manufacturing that utilizes for the method for metal-organic framework material.
Background technology
Metal-organic framework material is by the crystal of the organic bases part of metal ion and aromatic acid or nitrogenous, oxygen by coordinate bond self-assembly, based on the diversity of metal ion and organic ligand molecule, thus by the crystal of its molecule level design different pore size and topological framework, and the functionalization of porous material is realized by modes such as the introducings in Organic ligand modification and the open site of metal.As compared to porous materials such as traditional zeolite, porous silicon and gacs, as the metal-organic framework material of novel porous materials owing to having the specific surface area of super large, adjustable pore passage structure and abundant topological framework, can be used for the adsorption cleaning etc. of hydrogen, the storage of methane equal energy source gas, the capturing of carbonic acid gas isothermal chamber gas, the separation of hydro carbons, water pollution improvement and obnoxious flavour.
The source metal of current synthetic metals organic framework materials is mainly metal-salt and metal oxide etc., and these metallic compound production technique relative complex, energy consumption is higher, and causes environmental pollution.Flyash is a kind of solid waste that fuel-burning power plant fire coal produces afterwards, and its main component comprises oxygen, aluminium, silicon, iron etc.Single Pollution source maximum in polluting as China's industrial solid castoff, causes the impact of damage type to a great extent on human health and ecotope.And be rich in the element such as silicon, aluminium due to flyash, being thus used to extract aluminum oxide and white carbon black etc. in recent years, how for the resource utilization of flyash seeks more path for transformation, is problem demanding prompt solution.
Summary of the invention
In view of this, the invention provides a kind of coal ash for manufacturing that utilizes for the method for metal-organic framework material, to be intended to utilize in flyash the composition such as aluminium, iron as source metal to prepare metal-organic framework material.
The technical solution used in the present invention is specially:
Utilize coal ash for manufacturing for a method for metal-organic framework material, comprise the steps:
Flyash dissolving step: after flyash is fully ground and mixed in hydrochloric acid, fully stir or supersound process until after aluminium in flyash and dissolved ferric iron, make filtration treatment; In filtrate, add certain iron powder, fully stirring or supersound process are until iron powder dissolves, and the ferric ion in filtrate is reduced;
Crystal aluminum chloride obtains step: be heated to 30 ~ 85 DEG C to the solution that ferric ion is reduced, in the process of solvent evaporation, namely adularescent crystal is separated out, continuing heating makes white crystal continue to separate out, until when pale green crystals starts to separate out, adding water makes light green crystallization just dissolve, filtration is carried out to the solidliquid mixture containing white crystal and obtains white crystals and filtrate, by the white crystals salt acid elution obtained;
Iron protochloride tetrahydrate obtains step: the filtrate obtained carrying out cools until light green crystallization; After light green crystallization, further filter liquor, obtains light green crystallization, by the light green crystallization salt acid elution obtained;
Metal-organic framework material obtains step: be placed in autoclave by mixing with organic ligand and water or organic solvent respectively with the white crystals after salt acid elution, light green crystallization, heat treated 8 ~ 72h at the temperature of 40 ~ 220 DEG C, products therefrom after filtration, washing and drying treatment after, namely obtain aluminium based metal organic framework materials and ferrous metals organic framework materials respectively.
At the above-mentioned coal ash for manufacturing that utilizes in the method for metal-organic framework material, the quality of described iron powder is 0.5% ~ 7% of flyash quality.
At the above-mentioned coal ash for manufacturing that utilizes in the method for metal-organic framework material, the concentration of washing hydrochloric acid is 8 ~ 12mol/L.
At the above-mentioned coal ash for manufacturing that utilizes in the method for metal-organic framework material, described organic ligand is the aromatic acid of at least two teeth or the heterogeneous ring compound containing nitrogen, oxygen.
At the above-mentioned coal ash for manufacturing that utilizes in the method for metal-organic framework material, described organic solvent is one or several in carboxylic acid derivative, alkane, hydrochloric ether, alcohol compound, ketone compounds, pyridine compounds and their or ester compound.
The beneficial effect that the present invention produces is:
The abundant composition such as aluminium, iron contained in flyash is developed as source metal, reduce its to the pollution of environment while the application extension recycled to the preparation of metal-organic framework material, raw material is cheap and easy to get; And metal-organic framework material prepared by method of the present invention has larger specific surface area, there is higher actual application value.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail.
Utilize coal ash for manufacturing for a method for metal-organic framework material, its concrete steps are as follows:
S1: after fully being ground by flyash and mixed in hydrochloric acid, fully stirs until after the effective constituent such as aluminium, iron in flyash dissolves, make filtration treatment; In filtrate, add a small amount of iron powder (0.5% ~ 7% of flyash quality) stirs until iron powder dissolves, with the ferric ion reduced in filtrate;
S2: be heated to 30 ~ 85 DEG C to dissolving gained solution and make it evaporate, visible white crystallization (crystal aluminum chloride) is separated out; Keep constant temperature heating to make solution continue evaporation, until stop heating when light green crystallization (iron protochloride tetrahydrate) is separated out, add water and light green crystallization is dissolved just;
S3: the solidliquid mixture of S2 gained is filtered, the white crystals concentration obtained is concentrated hydrochloric acid (all adopting about 12mol/L in the embodiment) washing of 8 ~ 12mol/L; Obtained filtrate is cooled, until light green crystallization; By obtained light green crystallization salt acid elution; Why take the sequence of steps of " separate out white crystals → precipitation light green crystallization → dissolving light green crystallization → acquisition white crystals → cooling and obtain light green crystallization ", instead of " heating → separate out white crystals → acquisition white crystals; Heating → separate out light green crystallization → acquisitions light green crystallization " mode, be that minimizing mixes in order to allow white crystals and light green Crystallization Separation better.
S4: the white crystals after washing, light green crystallization are mixed with organic ligand and water or organic solvent respectively and is placed in autoclave, heat treated 8 ~ 72h at the temperature of 40 ~ 220 DEG C, heat treated products therefrom after filtration, washing and drying treatment after, namely obtain aluminium based metal organic framework materials and ferrous metals organic framework materials respectively.
Organic ligand used in step S4 is be at least the aromatic acid of two teeth or heterogeneous ring compound that is nitrogenous, oxygen; Organic solvent comprises the carboxylic acid derivative such as DMF, N,N-dimethylacetamide, N, N-diethylformamide; The alkane such as benzene, toluene; The hydrochloric ethers such as chlorobenzene; The alcohol compounds such as ethanol, ethylene glycol, glycerol; The ketone compounds such as acetone; Pyridine compounds and their; Ester class; Or certain or certain several mixture of these organic solvents or also can be the mixture of organic solvent and water.
Embodiment 1
Get flyash 25g and be placed in the hydrochloric acid that 250ml massfraction is 18%, filter after abundant stirring and dissolving, 1g iron powder is added until it is slowly heated to 80 DEG C after fully dissolving make solution evaporation in filtrate, adularescent crystal is separated out gradually, keep constant temperature heating to make solution evaporation, until add 3ml water when there is pale green crystals, pale green crystals is dissolved again;
Filtration washing obtains white crystal.White crystal, terephthalic acid are mixed according to mass ratio 120:166:765 with water, 220 DEG C are heated in autoclave, keep 72h, cooled and filtered obtains MIL-53 (Al) crystal, through the N of 80 DEG C, after dinethylformamide (DMF) washs 48h, drying, 300 DEG C of calcining 20h activation treatment, the specific surface area recording its Langmuir is 1497.1m
2/ g;
Cooling process is carried out until pale green crystals separates out rear filtration washing to filtrate.By pale green crystals, 2,5-dihydric para-phthalic acid, dimethyl formamide (DMF) and Virahol mix according to mass ratio 5:2:470:14,120 DEG C are heated under nitrogen atmosphere in reactor, keep 20h, cooled and filtered obtains MOF-74 (Fe) crystal, filter after the DMF washing at 120 DEG C, after methyl alcohol exchange activation 4d, drying treatment, the specific surface area recording its Langmuir is 904.3m
2/ g.
Embodiment 2
Get flyash 25g and be placed in the hydrochloric acid that 250ml massfraction is 18%, filter after abundant stirring and dissolving, 1g iron powder is added until be slowly heated to 70 DEG C after fully dissolving to make solution evaporation in filtrate, adularescent crystal is separated out gradually, keeping constant temperature heating to make to add 3ml water during solution evaporation pale green crystals to appear makes pale green crystals again dissolve, filtration washing obtains white crystal, by white crystal, the amino terephthalic acid of 2-mixes according to mass ratio 24:18:275 with water, 150 DEG C are heated in autoclave, keep 6h, cooled and filtered obtains NH
2-MIL-53 (Al) crystal, after the activation treatment that the DMFs of 80 DEG C (DMF) wash 48h, 150 DEG C of calcining 6d, recording its Langmuir specific surface area is 1086.1m
2/ g.
Cooling process is carried out until pale green crystals separates out rear filtration washing to filtrate.By pale green crystals, 2,5-dihydric para-phthalic acid, dimethyl formamide (DMF), isopropyl alcohol and water mix according to mass ratio 400:200:18:1:1,105 DEG C are heated in reactor, keep 20h, cooled and filtered obtains MOF-74 (Fe) crystal, filter after the DMF washing at 120 DEG C, after methyl alcohol exchange activation 4d, drying treatment, the specific surface area recording its Langmuir is 913.2m
2/ g.
Explain embodiments of the invention above, embodiment is herein used to provide a further understanding of the present invention.Obviously; the foregoing is only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; any be to one skilled in the art can expect easily, do not depart from change of the present invention or replacement in fact, be also all included within protection scope of the present invention.
Claims (5)
1. utilize coal ash for manufacturing for a method for metal-organic framework material, it is characterized in that, comprise the steps:
Flyash dissolving step: after flyash is fully ground and mixed in hydrochloric acid, fully stir or supersound process until after aluminium in flyash and dissolved ferric iron, make filtration treatment; In filtrate, add certain iron powder, fully stirring or supersound process are until iron powder dissolves, and the ferric ion in filtrate is reduced;
Crystal aluminum chloride obtains step: be heated to 30 ~ 85 DEG C to the solution that ferric ion is reduced, in the process of solvent evaporation, namely adularescent crystal is separated out, continuing heating makes white crystal continue to separate out, until when pale green crystals starts to separate out, adding water makes light green crystallization just dissolve, filtration is carried out to the solidliquid mixture containing white crystal and obtains white crystals and filtrate, by the white crystals salt acid elution obtained;
Iron protochloride tetrahydrate obtains step: the filtrate obtained carrying out cools until light green crystallization; After light green crystallization, further filter liquor, obtains light green crystallization, by the light green crystallization salt acid elution obtained;
Metal-organic framework material obtains step: be placed in autoclave by mixing with organic ligand and water or organic solvent respectively with the white crystals after salt acid elution, light green crystallization, heat treated 8 ~ 72h at the temperature of 40 ~ 220 DEG C, products therefrom after filtration, washing and drying treatment after, namely obtain aluminium based metal organic framework materials and ferrous metals organic framework materials respectively.
2. the coal ash for manufacturing that utilizes according to claim 1 is for the method for metal-organic framework material, it is characterized in that, the quality of described iron powder is 0.5% ~ 7% of flyash quality.
3. the coal ash for manufacturing that utilizes according to claim 1 is for the method for metal-organic framework material, it is characterized in that, the concentration of washing hydrochloric acid is 8 ~ 12mol/L.
4. the coal ash for manufacturing that utilizes according to claim 1 is for the method for metal-organic framework material, it is characterized in that, described organic ligand is the aromatic acid of at least two teeth or the heterogeneous ring compound containing nitrogen, oxygen.
5. the coal ash for manufacturing that utilizes according to claim 1 is for the method for metal-organic framework material, it is characterized in that, described organic solvent is one or several in carboxylic acid derivative, alkane, hydrochloric ether, alcohol compound, ketone compounds, pyridine compounds and their or ester compound.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105977040A (en) * | 2016-07-18 | 2016-09-28 | 南昌航空大学 | Metal organic skeleton electrode material of supercapacitor and preparation method of the electrode material |
| CN110655342A (en) * | 2019-09-03 | 2020-01-07 | 浙江大学 | Modified red mud capable of absorbing, curing and sealing carbon dioxide and preparation method thereof |
| CN110683780A (en) * | 2019-09-03 | 2020-01-14 | 浙江大学 | Modified fly ash for curing and sealing carbon dioxide and preparation method thereof |
| CN111921528A (en) * | 2020-06-28 | 2020-11-13 | 济南大学 | Method and system for preparing slurry bed Fischer-Tropsch synthesis catalyst slurry by pyrolyzing MOFs |
| WO2021022938A1 (en) * | 2019-08-02 | 2021-02-11 | 北京科技大学 | Method for preparing metal-organic framework using solid waste from metallurgical mine |
| CN113234234A (en) * | 2021-06-02 | 2021-08-10 | 中国矿业大学(北京) | Method for preparing aluminum-based metal-organic framework material by using high-alumina fly ash |
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- 2015-05-28 CN CN201510284334.0A patent/CN104961757A/en active Pending
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